CN1042160A - Prepare the elastomeric method of high molecular weight ethylene a-olefin with metallocene alumoxane catalyst - Google Patents

Prepare the elastomeric method of high molecular weight ethylene a-olefin with metallocene alumoxane catalyst Download PDF

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CN1042160A
CN1042160A CN89106344A CN89106344A CN1042160A CN 1042160 A CN1042160 A CN 1042160A CN 89106344 A CN89106344 A CN 89106344A CN 89106344 A CN89106344 A CN 89106344A CN 1042160 A CN1042160 A CN 1042160A
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zirconium
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luxuriant
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埃尔文·林·霍尔
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ExxonMobil Chemical Patents Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/904—Monomer polymerized in presence of transition metal containing catalyst at least part of which is supported on a polymer, e.g. prepolymerized catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Abstract

The preparation method of high molecular weight ethylene-alpha-olefin elastomerics, particularly ethylene-propylene elastomeric, required monomer carries out liquid polymerization in the presence of metallocenes/alumoxane catalyst system.Preferred method is a slurry polymerization process, uses the metallocenes/alumoxane catalyst that is carried on the silica-gel carrier, uses the excessive 'alpha '-olefin monomers that remains on liquid state to make polymerization diluent.Metallocenes component in the used catalyzer of present method is shown in following general formula.More preferably, the zirconium on the carrier is luxuriant/and alumoxane catalyst and ethene or another kind of olefinic polymerization generate the granules of catalyst of spheric good fluidity, obtain the granular elastomer product of good fluidity by slurry polymerization.

Description

Prepare the elastomeric method of high molecular weight ethylene a-olefin with metallocene alumoxane catalyst
The present invention relates to the preparation method of high molecular weight ethylene-alpha-olefin elastomerics, particularly ethylene-propylene elastomeric, promptly in the presence of zirconium, titanium or hafnium metallocene/Lv oxane catalyst system, by required monomeric liquid polymerization preparation.Preferable methods is a slurry polymerization process, makes carrier with the luxuriant/Lv of zirconium oxane catalyzer, silica gel, and uses the excessive 'alpha '-olefin monomers that remains on liquid state as polymerization diluent.More preferably, the luxuriant/Lv of the zirconium on carrier oxane catalyzer and ethene or another kind of alkene prepolymerization generate the free-pouring granules of catalyst of spheric, make the particle elastomerics of good fluidity by slurry polymerization.
The those of skill in the art in present technique field know, homopolymerization or copolymerization to alpha-olefin, various methods and catalyzer are arranged, for example, the polymerization of known ethene or propylene, can carry out polymerization separately or carry out polymerization production plastics in the presence of a small amount of other monomers, these plastics particularly can be used for such as application such as blowing, injection moulding, extrusion coating, film, sheet material, tubing, electric wire and cables.And for example, copolymerization of ethylene, propylene and also can with the 3rd monomer for example the non-conjugated diene polymerized hydrocarbon prepare elastomerics.Because the weathering quality of ethylene-propylene elastomeric, good resistance to heat aging and with mass filler and softening agent bonded ability, therefore have widely and use.It is scatterer, heater hose, vacuum piping, weather strip and sponge gasket that typical automobile is used.Typical industrial application is a sponge member, pad and tightness system.
Because their character is different with end-use, therefore the difference of making clear between the various factors of the elastomer performance that influences alpha-olefinic polymer and plastics performance is crucial, many factors and very complicated are arranged, but one of main correlative factor is and the monomer sequence of the whole polymer chain relevant factor that distributes.
For polyolefin plastics, owing to mainly have a kind of monomer in the polymer chain, so sequence distributes to almost not influence of polymer property.So in plastic copolymer, most of monomer will exist with long-chain monomer block.
When the sequence distribution is had little or nothing to do with the plasticity of polymkeric substance, then think the determinative relevant with elastomerics.If olefinic monomer trends towards forming the long block of energy crystalline, then the elasticity of polymkeric substance is poorer than having short monomer segmental polymkeric substance in the chain.
For example, the titanium catalyst that can produce stereospecific propylene sequence is disadvantageous especially, produces unwanted degree of crystallinity in the elastomerics because ethene that generates or propylene block will make.
Given comonomer is formed, and sequence distributes mainly to form with selected catalyzer and changes.This shows that the skilled worker must extremely carefully select to be used to prepare elastomeric catalyst system, they are determinatives that sequence distributes.On the other hand, prepare thermoplastic polymer as can be seen, the selecting catalyst system is not limited by these yet.
For fear of the degree of crystallinity of multipolymer, must use the catalyzer that can produce the material that narrow composition distributes, make and contain a kind of monomeric composition of high-content and do not exist.
And well-known, when the preparation ethene-alpha-olefin copolymer, alpha-olefin can play chain-transfer agent.For the low multipolymer of crystalline basically of alpha-olefin content, alpha-olefin can be ignored to the effect that changes molecular weight.Yet when preparation had the multipolymer of elastomerics scope composition, the catalyzer that can prepare the high molecular plastic copolymer was but produced the low-molecular weight polymer that is not suitable for the elastomerics application.In similar method for making, can produce undesirable molecular weight distribution variation or form changes in distribution.
Consider that polymkeric substance is formed and catalyst performance between complicated and people and uncomprehending both sides relation, if a kind of catalyzer only was used to prepare plasticity homopolymer or multipolymer in the past, the skilled worker is difficult to this catalyzer of prophesy to how producing elastomeric characteristic so.
European patent disclose 206794 disclose certain metal luxuriant/the aluminoxane system, particularly two (cyclopentadienyl) transition metal metalloceness, wherein the cyclopentadienyl ligand is unsubstituted or substituted and can passes through an alkylidene group or a silicylene bridging, can be used for ethylene homo, perhaps in order to improve ethene polymers transparency of products and impact property, the copolymerization that can be used for ethene and alpha-olefin makes multipolymer.
The prior art is pointed out the production of the luxuriant/Lv of amorphous ethylene-propylene copolymer available metal oxane catalyst system, and wherein the composition metallocenes is a kind of metallocenes of particular types.The term that uses in this prior art " EPC " is meant the multipolymer of ethene and alpha-olefin, and this multipolymer presents the elastomer performance that rubber had of ASTM D1566 definition.Yet as reporting up to now, the EPC molecular weight of Sheng Chaning is too low like this, is not suitable for use in the ordinary elasticity material, and is particularly especially true when elastomerics contains greater than the 20wt% propylene.For produce the product that contains the small amount of residual catalyzer in an appropriate time, the activity of catalyst system therefor is too low simultaneously.
European patent discloses 128046 and points out Lv oxane system and dimethyl silicylene dicyclopentadienyl zirconium dichloride or two (cyclopentadienyl) phenylbenzene titanium energy catalytic production lower molecular weight EPC, and such catalyst system can use together with the metallocenes/Lv oxane catalyst system of other different in kinds, produce the reaction mixture of EPC and high density polyethylene(HDPE) (HDPE) and linear low density of polyethylene (LLDPE), for example HDPE/EPC, LLDPE/EPC, HDPE/LLDPE/EPC reaction mixture or analogue.EPC component in the mixture that makes like this-because its molecular weight is low, itself be not a kind of industrial useful elastomerics-but be used for base-material HDPE or LLDPE(and EPC co-production) the properties-correcting agent mixed composition be fine.
Japanese publication number 119215,121707 and 121709 discloses the production of various ethene-alpha-olefins, propylene-alpha-olefin, 1-butene-alpha-olefin flexible copolymer, use metallocenes/Lv oxane catalyst system, wherein metallocenes is two (cyclopentadienyl), the metal-salt of two (indenyls) or two (tetrahydro indenyl) compound of low-grade alkylidene bridging.This day disclosure explanation copolymer product can be produced with gas phase or liquid phase reaction method, has very wide performance range, and for example degree of crystallinity from 0.5 to 60%, and molecular weight distribution (MWD) reaches a spot of boiling methyl acetate solubility component less than 3.This day the disclosure such copolymerization has been described can be in the presence of such catalyzer, from-80 to 50 ℃ of temperature, pressure is from the normal pressure to 30kg/cm 2Carry out in the scope.Yet, in two day embodiment of the present disclosure, the actual production of these materials has been described, described reaction conditions is: temperature-10 is to-20 ℃, and reaction times 5-30 hour, use solution polymerization process, make solvent with toluene.The described method of two days embodiment of the present disclosure is because long reaction time, temperature low and need be from polymer solvent the separation of polymeric product, the production cost of gained copolymer material is sharply increased, thereby does not cause the interest of large-scale commercial production.Day disclosure 121709 described methods are because toluene is made solvent, the separation of a large amount of solvents and the expense of recirculation, thereby do not cause the attention of large-scale commercial production yet.
Use metallocenes/Lv oxane catalyst system, in being suitable for industrial Reaction conditions range, the satisfied elastomeric method of EPC of character does not also obtain discussing on the manufacture.For the EPC elastomerics of character with industrial satisfaction, its mooney viscosity (ML 1+8At 127 ℃) should be not less than 10, weight-average molecular weight is not less than 110,000, and second-order transition temperature is lower than-40 ℃, and degree of crystallinity is not more than 25%.Some is used as extrusion characteristics, and the elastomeric weight distributing characteristic of EPC is a weight-average molecular weight and the ratio of number-average molecular weight should be 5 or littler.Should produce the EPC elastomerics under these conditions: from 0 to 80 ℃ of temperature of reaction, the reaction times, Reaction conditions range was most economical less than 6 hours, was industrial enforceable therefore.In order to separate the polymerisate of final commercial form, usually need additional treatment step, require reaction conditions should make the number of this additional treatment step reduce to minimum or save.Therefore require to use one or more monomers, rather than use the inert solvent that therefrom to isolate polymkeric substance afterwards to make thinner as reaction diluent.For the ease of separation and processing subsequently, also require products therefrom to be suspended in the reaction medium with particle form.Require catalyzer to have enough activity at last, do not need from product, to remove catalyst residue (deashing).
The present invention includes a kind of method, this method is used metallocenes/aluminoxane catalyst system, wherein metallocenes is that the zirconium of particular types is luxuriant, titanium is luxuriant or hafnium is luxuriant, for giving security being suitable for producing high molecular weight ethylene-alpha-olefin elastomerics under the industrial reaction conditions.In the slurry reaction method, in metallocenes/aluminoxane catalyst system, use a kind of special metallocenes, preferably zirconium is luxuriant, produces the high molecular weight ethylene-alpha-olefin elastomerics of typical low ash content (ash content is meant catalyzer and the co-catalyst residue in the polymkeric substance), does not need de-ash.
The metallocenes component of the metallocenes/aluminoxane catalyst system that uses in enforcement the inventive method has general formula:
M is zirconium, titanium or hafnium in the formula; Each R 1Represent C respectively 1-C 20Linear, side chain or cyclic alkyl maybe can form the C of condensed ring 2-C 4The ring alkylidene group; R 2Be C 1-C 6Linear, side chain or cyclic alkylidene group, Si 1-Si 2The inferior silicon-carbon alkyl that silicylene that alkyl replaces or alkyl replace; Each X represents halogenide, hydride, oxo bridge or alkyl such as aryl or linear, side chain or the cyclic alkyl in the metallocenes dimer respectively; " Y " is 2,3 or 4, and " b " is 0 or 1.Preferred L is a zirconium.The typical X alkyl can comprise 1 to 20 carbon atom, but as needs to contain more carbon atoms.
Preferred catalyst system has following general formula:
M, X, R in the formula 1, R 2The same with the definition of b, Z is 0,1 or 2.Most preferred catalyzer is that M is a zirconium, and " b " is 1 and R 2The catalyzer of the logical formula II of the silicylene that replaces for alkyl.
In metallocenes/aluminoxane catalyzer, use the metallocenes of determining to implement the present invention, metallocenes in the hydrocarbon solution and aluminoxane can be added in the polymerisation diluent, implement present method with the catalyzer of carrier free form.Preferably use metallocenes/aluminoxane catalyst system with heterogeneous form at (on silica-gel carrier) on the support of the catalyst, carry out polyreaction with slurry polymerization technique, wherein use the 'alpha '-olefin monomers that is suitable for use as polymerisation diluent excessive and that be in liquid state.Be meant that with " slurry " polymerization the polymerisate that makes is suspended in the polymerization diluent with particle form.More preferably, in order directly to obtain particle EPC product from slurry process, the luxuriant/Lv of metal oxane catalyzer and ethene or a kind of alpha-olefin prepolymerization are with control EPC granularity and size-grade distribution.
The invention relates to the elastomeric method of high yield ethene-alpha-olefin of production high molecular, low-crystallinity and low ash, particularly about containing the catalyst system of metallocenes/Lv oxane system, this catalyst system has high reactivity to produce high molecular weight ethylene-alpha-olefin elastomerics with slurry polymerization process.
Term " EPC " is meant the ethene that presents elastomer performance and the multipolymer of alpha-olefin as used herein.Be applicable to ethene and prepare preferably C of elastomeric alpha-olefin 3-C 16Alpha-olefin.The indefiniteness example of these alpha-olefins is propylene, butene-1, amylene-1, hexene-1, octene-1 and dodecylene-1, can mix as needs and use more than one alpha-olefins.
The EPC elastomerics can contain the 20-90% weight ethene of having an appointment, even more preferably about 30-85% weight ethene, more preferably about 35-80% weight ethene.
The catalyzer that method of the present invention is used is a metallocenes/Lv oxane system, and wherein the metallocenes component of catalyst system has
M is zirconium, titanium or hafnium in the formula; R 2Bridging group if present, is linear, side chain or the cyclic alkylidene group with 1 to 6 carbon atom, silicylene or the Si with alkyl replacement of 1 to 2 Siliciumatom (replacing the carbon atom in the bridge) 1-Si 2The inferior silicon-carbon alkyl that alkyl replaces; Each R 1Be respectively the alkyl linear or side chain with 1 to 20 carbon atom, perhaps carbon atom is connected on the different ring position of cyclopentadienyl and forms C 4-C 6The cyclic olefin double-basis of condensed ring system; Each X is respectively hydride, halogenide, the dimeric oxo bridge of metallocenes or alkyl such as aryl or linear, side chain or cyclic alkyl; " Y " is that 2 to 4 number, " b " are 0 or 1.Preferred metallocenes is that M is that the zirconium of zirconium is luxuriant.Typical R 1Alkyl is methyl, ethyl, propyl group, butyl, amyl group, isopentyl, hexyl, isobutyl-, heptyl, octyl group, nonyl, decyl, hexadecyl, 2-ethylhexyl, phenyl or the like.Typical R 1The alkene double-basis is ethene, propylene, butylene or similar alkene.Preferred R 1Base is that the cyclic olefin butylene is connected to and forms tetrahydroindene condensed ring structure on the adjacent ring position of cyclopentadiene.Therefore, in the preferred case, the metallocenes component of catalyst system is that zirconium is luxuriant, general formula is:
R in the formula 1It is the alkyl linear or side chain of 1 to 20 carbon atom; " Z " is 0 to 2 integer, R 2, X and " b " be ditto described.Typical R 2Linear alkylidene group is methylene radical, ethylidene, propylidene, butylidene, pentylidene, hexylidene or the like.Typical R 2Ring alkylidene group two bases are ring butylidene, ring pentylidene, cyclohexylene etc.Typical R 2The silicylene that alkyl replaces is dimethyl silicylene, methylethyl silicylene, diethyl silicylene, tetramethyl-two silicylene, tetraethyl-two silicylene or the like.R 2Also can be the inferior silicon-carbon alkyl that alkyl replaces, i.e. the bridge formed of carbon-silicon chain, for example-Si(R ') 2-C(R ") 2-, R ' is a low alkyl group in the formula, R " is hydrogen or low alkyl group.Typical R 2The inferior silicon-carbon alkyl that alkyl replaces is a 1-silicon-1,1-dimethyl ethylidene, 2-silicon-2,2-dimethyl propylidene, 1,3-two silicon-1,1,3,3-tetramethyl-propylidene etc.Preferred R 2Be that ethylidene, dimethyl silicylene or " b " are 0, no R 2; Most preferred R 2It is the dimethyl silicylene.
Luxuriant two (tetrahydro indenyl), ethylidene-two (tetrahydro indenyl) and dimethyl silicylene-two (tetrahydro indenyl) ligand of comprising of preferred zirconium, wherein the dimethyl silicylene-two (tetrahydro indenyl) zirconium is luxuriant is most preferred.Representational suitable zirconium is luxuriant to be two (tetrahydro indenyl) zirconium dichlorides of two (tetrahydro indenyl) zirconium dichlorides, ethylidene bridging and two (tetrahydro indenyl) zirconium dichlorides of dimethyl silicylene bridging.
The method for preparing required metallocenes component is known in the prior art, for example can be referring to H.H.Brintzinger etc., and Journal of Organometallic Chemistry, 288 volumes, 63 pages (1985); C.S.Bajgur, W.R.Tikkanen, J.L.Petersen; Inorg.Chem., 24 volumes, 2539-2546 page or leaf (1985).
De Lv oxane is a kind of oligomeric aluminum compound in the catalyst system, and it can be the general formula (R-Al-O) ring compound represented of n, or general formula
R(R-Al-O) nAlR 2The linear compound of expression.In the Zai Lv oxane general formula, R is C 1-C 5Alkyl, for example methyl, ethyl, propyl group, butyl or amyl group and " n " they are 0 to about 50 integers, preferred R is that methyl and " n " are at least 4.The aluminium oxane can be used prepared in various methods well known in the prior art, and for example, aluminum alkyls can perhaps can contact as the hydrated copper sulfate that is suspended in the inert organic solvents with a kind of salt hydrate with the water treatment of dissolving in the inert organic solvents, forms the aluminium oxane.But usually the product of aluminum alkyls and limited amount water reaction generation is linear and mixture cyclic Lv oxane.
The catalyzer that uses in the inventive method is by metallocenes, and preferably zirconium is luxuriant (as a kind of specific component) Yu the mixture of Lv oxane preparation.This catalyst system can with required metallocenes and aluminium oxane in suitable diluent monomer is arranged or do not have in the presence of the monomer mixed, as a kind of unsupported catalyst.Use the polyreaction of unsupported catalyst to implement with solution polymerization or slurry polymerization thing.Within the scope of the present invention, this catalyst system promptly absorbs required metallocenes with Lv oxane component prepares with catalyst support material such as silica gel, aluminum oxide or other suitable inorganic carrier materials preferably with preparation of heterogeneous catalyst form and use.
Heterogeneous catalyst system is specially adapted to slurry polymerization process, and the method according to this invention is for preparing the EPC elastomerics, preferably using liquid alpha-olefin to make polymerization diluent.Because the actual restriction of using, slurry polymerization carries out in liquid diluent, and polymerisate is insoluble to wherein basically.The thinner that is used for slurry polymerization preferably is less than one or more hydro carbons of 5 carbon atoms, as needs, can all or part of use saturated hydrocarbons such as ethane, propane or butane make thinner; Equally, also can all or part of use 'alpha '-olefin monomers or the mixture of different 'alpha '-olefin monomers make thinner; Most preferred thinner mainly contains 'alpha '-olefin monomers or wants the polymeric monomer.
The solid support material that is applicable to the preparation heterogeneous catalyst is any finely powdered inoganic solids porous support, for example talcum, silicon-dioxide, aluminum oxide, cimita or their mixture, other inorganic oxides that can use separately or be used in combination with silicon-dioxide or cimita are magnesium oxide, titanium oxide, zirconium white etc.As known in the art, inorganic oxide should dewater and remove moisture content, if desired, can by other heating or with such as the reaction of deshydroxy bases such as lithium alkylide, chloro silicomethane, aluminum alkyls or preferred aluminium oxane, remove surface hydroxyl residual in the inoganic solids porous support.Support of the catalyst is to use the aluminium oxane preferably, and the dehydration inorganic oxide that the most handy methyl aluminium oxane was handled is more preferably the dehydration silica gel of handling with methyl aluminium oxane.
As heterogeneous carried catalyst,, the conventional luxuriant He Lv of hydro carbons soluble metal oxane makes by being deposited on the solid support material (as the dehydration silica gel of handling with methyl Lv oxane).The silica gel particle size range that is suitable for is the 1-600 micron, is preferably the 10-100 micron, and surface-area is the 50-1000 meters squared per gram, is preferably the 100-500 meters squared per gram, and pore volume is 0.5-3.5 centimetre 3/ gram.Silica gel can be at 100-1000 ℃, preferably 300-800 ℃ thermal treatment 1-100 hour, preferably 3-24 hour, use with dehydrated form to guarantee it.
This catalyst system can make with contacting of Lv oxane by metallocenes before these components are added reactor, perhaps, also can prepare in reactor on the other hand.Use zirconium luxuriant and form under the situation of reactive systems in reactor, the requirement of the mol ratio of Al and Zr is 20-4000, preferably 20-1000 in the 10-5000 scope preferably in the reactor.Be that reactor forms under the situation of reactive systems outward, the preferred proportion of Al and Zr is 1-200, more preferably 20-200.Can use overall proportion that additional Lv oxane promotor makes Al and Zr in this case in the 10-5000 scope, be preferably in the 20-4000 scope, preferably 20-1000.Simultaneously, in order to remove any impurity that exists in the reactor, a small amount of another kind of alkylaluminium cpd such as triethyl aluminum or triisobutyl aluminium can be added in the reactor with additional Lv oxane, or replace additional Lv oxane.Under above-mentioned all situations, catalyzer or promotor can be in reactor with suitable carriers on a kind of component contact (as described below).
As mentioned above, specific zirconium is luxuriant is preferred metallocenes.Therefore, mainly be luxuriant to the further discussion of catalyzer about zirconium, obviously, similarly condition and method are applicable to that also titanium is luxuriant and hafnium is luxuriant.
In a preferred embodiment, dehydration silica gel contacts Yu the Lv oxane, contacts with zirconium is luxuriant subsequently.If desired can carrier before the Lv oxane contacts earlier zirconium in the luxuriant solid support material that is added to dehydroxylation.According to the preferred embodiment of the invention, De Lv oxane is added on the carrier in the suitable varsol being dissolved in, this carrier is with the exsiccant form, or in hydrocarbon liquids identical or that another kind is suitable, form slurries, treat that preferably carrier is in a vacuum after the drying, in light hydrocarbon, form slurry more again, and then the adding zirconium is luxuriant in slurry.It is luxuriant to add the capacity zirconium in this slurry, and making the zirconium amount of metal is the 0.02-5.0% weight of total catalyst levels.More preferably should to make the zirconium amount of metal be the 0.10-1.0% weight of total catalyst levels to the luxuriant amount of the zirconium of Jia Ruing.
As mentioned above, the processing of solid support material is carried out in inert solvent.Can use identical or different inert solvents to dissolve the luxuriant He Lv of zirconium oxane.Preferred solvent is included in the various hydro carbons that are in a liquid state under treatment temp and the pressure, and various component can both be dissolved in wherein, and the examples of solvents that is suitable for comprises alkane, as propane, butane, pentane, iso-pentane, hexane, heptane, octane and nonane; Naphthenic hydrocarbon such as pentamethylene and hexanaphthene; Aromatic hydrocarbons, as benzene, toluene, dimethylbenzene, ethylbenzene and diethylbenzene.Should use sufficient solvent so that enough hot transfer agents to be provided, remove the right amount of each catalyst component in the dereaction and make good mixing.
In the reactant contact process, temperature can change in wide scope, for example can also can use higher or lower temperature from 0 °-100 ℃.Reaction between Lv oxane and the solid support material is very rapid, yet, it is desirable to the Lv oxane and contact eight hours about half an hour to ten or longer time with solid support material.Preferably being reflected at 25-100 ℃ kept about one hour.
No matter when, all must protect the catalyst component of each component and recovery to avoid oxygen and moisture, therefore be reflected in the atmosphere that does not have oxygen and moisture and carry out, and in the atmosphere that does not have oxygen and moisture, reclaim catalyzer.Reaction is preferably under exsiccant rare gas element such as the nitrogen existence to be carried out, and preserves the catalyzer that reclaims in this inert atmosphere.
The luxuriant He Lv of zirconium oxane is after deposition on the carrier finishes, the most handy small amounts of monomer such as ethene are handled this solid material, on the solid catalysis agent material, form an amount of polymkeric substance, make catalyst weight increase by 50% at least, it is desirable to about 100-500% of catalyzer and solid support material gross weight.Therefore, such processing is called the prepolymerization reaction of catalyzer.This solid material or can reclaim with any known technology through prepolymerized solid material, for example available filtration method, vacuum vapor deposition method or decantation reclaim the solid catalysis agent material from liquid.This solid is in pure dry nitrogen air-flow or carry out drying in a vacuum then.
The prepolymerization reaction of solid catalysis agent material helps to generate the EPC elastomer particles of strict control in slurry polymerization.Pre-polymerized catalyst can be with a kind of hydrocarbon drip washing, to obtain good particle.The prepolymerization reaction has significantly reduced the demand of Dui Lv oxane, for example when in the liquid phase that the Lv oxane is added to reactor, need Al in order to obtain the luxuriant ratio of high reactivity Lv oxane and zirconium: Zr is 1000: 1 or bigger, but when when the Lv oxane is added in the pre-polymerized catalyst, this ratio is just enough less than 100: 1.For pre-polymerized catalyst, the proportional range of aluminium and zirconium preferably from about 20: 1 to 100: 1, and still obtained high reactivity from about 1: 1 to 500: 1.
More preferably carried catalyst prepares with following method: 1) (be added to as toluene) De Lv oxane and form slurries in the carrier being dissolved in suitable solvent; 2) stirred these slurries 30-60 minute at 60-80 ℃; 3) fully add the heat extraction solvent in a vacuum, obtain dried powder; 4) add a kind of light hydrocarbon (for example pentane), make this powder become slurry; 5) add the luxuriant solution in pentane or small amount of toluene of zirconium, and stirred 15-60 minute at 20-60 ℃; 6) with ethene or the prepolymerization in the pentane slurry of other alkene, collection then, drip washing and dry catalyst.For obtaining best particle shape, except De Lv oxane on pre-polymerized catalyst, had better not be added to the Lv oxane in the reactor.In order to remove the impurity in the charging, can add the capacity aluminum alkyls, as triethyl aluminum or triisobutyl aluminium, but inexcessive.
According to the preferred method of the present invention, prepare the EPC elastomerics with slurry polymerization process, use 'alpha '-olefin monomers or monomer mixture to make polymerization diluent, the luxuriant/Lv of carrier zirconium oxane catalyst system is suspended in wherein, in order in the EPC product, to obtain required ethylene content, should in reactor, add the ethene of q.s.The dividing potential drop of ethene depends on the structure that used zirconium is luxuriant, and this dividing potential drop surpasses the vapour pressure of 'alpha '-olefin monomers, can produce the product of predetermined ethylene content.Generally, at ethylene partial pressure from about 10-1000PSi, 40-600PSi preferably, polymerization diluent is maintained at about-10-100 ℃ temperature, preferably about 10-70 ℃, under most preferably about 20-60 ℃ condition, carries out polyreaction.Ethene and 'alpha '-olefin monomers copolymerization generate the EPC elastomerics under these conditions.
Polyreaction also available gap slurry polymerization and continuous slurry polymerization method is carried out.The continuous slurry polymerization method is better, and in the method, ethene, liquid alpha-olefin and catalyzer continuously add in the reactor, the EPC polymkeric substance that its quantity is discharged from reactor in equaling to produce, the amount of ethene, alpha-olefin and catalyzer.
For implementing method of the present invention, adopt following method, this method to scope of the present invention without any restriction: in stirred-tank reactor, add propylene liquid monomer, material ethylene gas, both can join the gas phase part of reactor, available again method well known in the prior art sprays in the liquid phase.Comprise in the reactor mainly by propylene liquid and dissolved ethylene gas liquid phase of forming and the gas phase that contains all monomer vapours.Catalyzer and promotor (and/or clean-out system aluminum alkyls) can add the gas phase or the liquid phase of reactor by nozzle.Temperature of reactor and pressure can pass through controls such as refluxed evaporator 'alpha '-olefin monomers (automatically refrigerating method) and spiral coil cooling tube, chuck.Polymerization rate is controlled by the cocatalyst concentration that catalyzer adds speed or use respectively.Ethylene content depends on the ratio of ethene and propylene in the luxuriant and reactor of the zirconium of use in the polymerisate, and this ratio is controlled by the relative adding speed that is added to the each component in the reactor.
As shown in table 1, for a given group reaction condition, have that the zirconium of a plurality of unlimited reactive sites is luxuriant to be combined with propylene easilier than the zirconium with a plurality of steric hindrance reactive sites is luxuriant.Bridge between the cyclopentadiene ring is short more, reactive site is unlimited more; Huge more, the response location of additional substituting group is obstructed more on the ring.In order to open wide response location, even on the cyclopentadiene ring, have the place of bulky substituent, preferably use minibridge between the ring, as dimethyl silicylene bridge.But luxuriant for any zirconium, compare, can change this combination by ethylene/propene in the conditioned reaction device.
As known in the art, polymer molecular weight can be controlled by the hydrogen stream of controlling other polyreaction variablees such as temperature or be added in the reactor gas phase.The polymerisate of staying in the reactor can reclaim by under reduced pressure flashing off gas ethene and propylene, and, if necessary, can in equipment (as the devolatilization forcing machine), carry out further devolatilization.Catalyzer residence time in reactor was generally about 20 minutes to 8 hours in continuous processing, was 30 minutes to 6 hours preferably, preferably 30 minutes to 4 hours.
With the elastomeric final performance of EPC and luxuriant structure of zirconium and reaction conditions that the inventive method is produced, particularly the ethylene/propene ratio is relevant with temperature of reaction.
Various zirconiums in the table 1 are luxuriant to present different activity to a given group reaction condition, as long as catalyzer can produce required polymer performance, active certainly higher catalyzer is better.Yet for their specific binding characteristics, active lower catalyzer also is preferred, and for example when the high ethylene content EPC of preparation, in order to reduce total reaction pressure, zirconium bridging or long bridging is luxuriant to be preferred.These catalyst lifes are very long, and catalyst concn is given regularly, but the EPC elastomerics of the reaction times production high yield of growing like this, and the catalyst residue amount of products therefrom is low.
Implement in the embodiments of the invention, in explanation in order to analyze the EPC elastomerics that makes, the analytical technology that use is narrated below.Mooney viscosity, ML 1+8, 127 ℃, according to ASTM D1646 Monsant Mooney viscometer determining.The polymkeric substance ethylene content is measured with infrared analysis according to ASTM D3900, according to the molecular weight of following technology, with Waters 150 gel permeation chromatography molecular weight and the molecular weight distribution that differential specific refractory power (DRI) detector and the online light-scattering photometer of Chromatix KMX-6 are housed with gel permeation chromatography (GPC) mensuration EPC elastomer product.This system uses down at 135 ℃, and with 1,2, the 4-trichloro-benzene is made moving phase, uses Shodex(Showa Denko America company limited) polystyrene gel post 802,803,804 and 805.In " Liquid Chromatography of Polymers and Related Materials III ", J.Cazes editor, Marcel Dekker has discussed this technology for 1981,207 pages, lists for reference at this.Hangover for post need not proofreaied and correct, but in general data are satisfied the criteria, for example the hydrogenation polyisoprene of (U.S.) State Bureau of Standardization polyethylene 1484 and negatively charged ion catalytic production (ethylene-propylene alternating copolymer) illustrates correction to Mw/Mn less than 0.05 unit, and Mw/Mn tried to achieve from the elution time.LALLS software with Beckman/CIS customization available on the market permeates subassembly together with standard gel, with Hewlett-Packard 1000 Computing, finishes data analysis.
Embodiment 1
Synthetic (the MAO/SiO of methyl Lv oxane/silica-gel carrier 2)
In a loft drier, the solution (by Ethyl company provided, Labels Were Marked with 1MAL) of 30 milliliters of methyl aluminium oxanes (MAO) in toluene is added to 15 grams in 800 ℃ of Davison 955 silica gel of dry 4 hours, under vacuum, remove and desolvate.
Embodiment 2
With silica gel is two (tetrahydro indenyl) zirconium dichloride catalyzer of carrier
Prepare the silica gel that MAO handles by embodiment 1 identical method, but add 25 milliliters of MAO(Ethyl companies, 1MAL) rather than 30 milliliters.The silica gel that the MAO that weighing 5g generates handles places the Schlenk flask that magnetic stirring apparatus is housed of loft drier.250 milliliters of two (tetrahydro indenyl) zirconium dichlorides are added in 7 milliliters of toluene, and this toluene solution is added drop-wise on the silica-gel carrier of MAO processing, magnetic agitation more than 30 minute.Solid block is held in both hands homogenizing after 5 minutes with stirring, and 6 milliliters of other toluene is added in the silica gel slurry again.Flask is moved on in the vacuum system from loft drier, and under vacuum, remove toluene.This drying solid contains 4.8% weight catalyst system or 1.1 weight zirconiums.
Embodiment 3
With silica gel is two (tetrahydro indenyl) zirconium dichloride catalyzer of the ethylidene bridging of carrier
In loft drier, take by weighing silica-gel carrier 20 grams that MAO that embodiment 1 makes handles, place 50 milliliters of Schlenk flasks that 1 inch long magnetic agitation is held in both hands are housed.50 milligrams of ethylenebis (tetrahydro indenyl) zirconium dichloride is dissolved in 3 milliliters of toluene (by means of heat gun).After the dissolving, this drips of solution is added on 2 silica gel handled of gram MAO, and then adds 4 milliliters of dry toluene, make powder become slurry.From loft drier, take out and in 55 ℃ of oil baths, stirred 30 minutes.The slurry of in the Schlenk system, finding time then.When complete drying, reclaim 1.834 the gram solids, have the luxuriant or 0.52wt% zirconium of 2.4wt% zirconium.
Embodiment 4
With silica gel is two (tetrahydro indenyl) zirconium dichloride catalyzer of dimethyl silicylene of carrier
In loft drier, the two drips of solution of (tetrahydro indenyl) zirconium dichloride in 3 milliliters of toluene of 50 milligrams of dimethyl silicylene are added in the silica gel that the MAO of 2 gram examples 1 handled, hold in both hands vigorous stirring with magnetic agitation.And then add 4 milliliters of toluene, make solid become slurry.This slurry stirred 30 minutes at 55 ℃, removed under vacuum then and desolvated.This catalyzer contains the luxuriant or 0.49wt%Zr of 2.4wt% zirconium.
Embodiment 5
The synthetic of pre-polymerized catalyst (is used for embodiment 9 test C 3)
Place 500 milliliters the flasks that magnetic agitation is held in both hands are housed in 5 gram Davison, 948 silica gel (spending 4 hours), add 85 milliliters of MAO toluene solutions (Ethyl company indicates 1MAL) 800 ℃ of dryings.Under vacuum, be heated to 45 ℃ and remove toluene.1.08 gram solid residues under the magnetic agitation in 25 milliliters of dry pentanes (have been used 10 milliliters of dry pentanes, use 4 milliliters of dry pentane drip washing then, filter after each drip washing) in add 11 milligrams of two (tetrahydro indenyl) zirconium dichlorides and be dissolved in 25 milliliters of solution in the dry pentane.These slurries at room temperature stirred 1 hour then.
Cool off reaction flask with water-bath, with 4 mmoles/minute speed add ethene, add 30 minutes.The collection powder is also dry on the sintered glass funnel in loft drier.Collect 4.37 gram pre-polymerized catalysts (being brown powder), several bigger polymkeric substance are arranged on the flask walls.This catalyzer contains 19wt% silicon-dioxide, 5.7wt% methyl Lv oxane, 0.25wt% zirconium luxuriant (0.057%Zr) and 75wt% polyethylene.Because this carried catalyst has only the 25wt% pre-polymerized catalyst, in the table III, indicate PP(400) THIZ, represent this catalyzer prepolymerization to its original weight 400% and contain tetrahydroindenyl zirconium luxuriant (THIZ).
Embodiment 6
The synthetic of pre-polymerized catalyst (is used for embodiment 9 test C 8)
Add the solution (5.5wt%AL) of 2500 milliliters of methyl Lv oxanes in toluene in 240 gram Davison, 948 silica gel (800 ℃ of dry mistakes) in being contained in 2 gal reactor that have mechanical stirrer.Spray into nitrogen and be heated to 80 ℃ and remove toluene.Reactor cooling to 25 ℃, powder drains the liquid above the sedimentary slurry with 2 liters of dried iso-pentane drip washing twice after each drip washing.Add 4 liters of iso-pentane then, make powder become slurry, and under vigorous stirring, restrain the two solution of (tetrahydro indenyl) zirconium dichloride in 300 milliliters of toluene with adding in more than 10 minutes 5.0.Temperature is controlled at and is lower than 30 ℃, adds ethene (with 1.5 hours) in the slurries that stirring.Make the slurries precipitation and move into loft drier, be placed on drying on the strainer, and be stored in the nitrogen.Collect 941 gram brown powder, it contains 24wt% silicon-dioxide, 6.9wt% methyl Lv oxane, 0.50wt% zirconium luxuriant (0.12wt%Zr) and 67wt% polyethylene.Because carried catalyst has only the pre-polymerized catalyst of 33wt%, in the table III, indicate PP(300) THIZ, the expression catalyzer by prepolymerization to its original weight 300% and to contain tetrahydroindenyl zirconium luxuriant.
Embodiment 7
The synthetic of pre-polymerized catalyst (is used for embodiment 10 test C 11)
To adding 200 milliliters of MAO toluene liquid (obtain from Ethyl company, indicate 1MAL) in 10 gram Davison, 948 silica gel in 500 ml flasks that magnetic agitation holds in both hands (800 ℃ of dryings 4 hours) are being housed.80 ℃ of heating were removed toluene after 1 hour under vacuum.2 gram solid residues stir at the vacuum lower magnetic force in 35 milliliters of dry pentanes, to wherein adding two (tetrahydro indenyl) zirconium dichlorides (STHI) of 40 milligrams of dimethyl silicylene that are dissolved in 3 milliliters of dried toluene.These slurries at room temperature stirred 15 minutes.
Cool off reaction flask with water-bath, with 6 mmoles/minute speed add ethene (adding 30 minutes), then on the sintered glass funnel of powder collection in being placed on loft drier, with 30 milliliters of dry pentanes washings three times and drying.Collect 6.17 the gram pre-polymerized catalysts, be brown powder, several bigger polymkeric substance are arranged on the flask walls, this catalyzer contains 12wt % methyl Lv oxane, 0.65wt% zirconium luxuriant (0.13wt%Zr) and 67wt% polyethylene.Because this catalyzer is aggregated to 308% of its original weight, therefore in the table III, indicate PP(308) STHI.
Embodiment 8
Standard unsupported catalyst polymerization: method A
Cleaning, exsiccant one liter autoclave are rinsed well with propylene, added the accurate MAO toluene solution of quantity (Ethyl company indicates 1MAL) with syringe.Then, adding ethene in the reactor raises reactor pressure.To be dissolved in 3 milliliters of luxuriant injection autoclaves of the accurate zirconium of the quantity in the toluene, begin reaction.Feed ethene and make maintenance original pressure in the autoclave.After the required time was carried out in reaction, washing out monomer and making temperature was 25 ℃.From reactor, reclaim 50 ℃ of dried overnight in polymerisate and the vacuum drying oven.The quantity of catalyst system therefor and type and polymerization result are listed in the table I.
Embodiment 9
Standard vector polymerization catalyst: method B
Imitate the identical method of example 8, just the catalyzer of carrierization is injected 3 milliliters of hexanes with the slurries form.Each tests used catalyzer composition, the amount of catalyzer and promotor, and temperature and ethylene pressure all are listed in the table II.
Embodiment 10
Standard pre-polymerized catalyst polymerization: method C
Imitate the identical method of example 9, just do not use Lv oxane promotor, and make the polyreaction clean-out system, be combined in that De Lv oxane provides unique promotor in the pre-polymerized catalyst with TEAL.Use the detailed description of pre-polymerized catalyst embodiment to be listed in the table III.
The table I is similarly illustrating the influence of the luxuriant structure of zirconiums to active and product performance with a series of tests under the condition.Active catalyst causes violent intensification when the reaction beginning, polymerisate always stains the reactor internal surface when using unsupported catalyst.Heat up both altogether when staiing reactor with beginning, make these tests be difficult to control, molecular weight distribution is broadened, the molecular weight of product reduction also is difficult to repeat.
However, the test of table I illustrates according to the present invention (A 10-A 16) the luxuriant texture ratio comparison catalyzer (A that has of most of zirconiums 1-A 9) active big and molecular weight of product height.Test A 7To A 9The comparison catalyzer obviously make an exception, these catalyst structures are different with structure of the present invention, the test A 7Under than higher activity, still make the good product of molecular weight; Yet such molecular weight has only by consuming a large amount of ethene and could obtain, and when ethylene content was low, this catalyzer can only obtain lower molecular weight, as test A 8And A 9Shown in.Clearly, test A 11-A 14The catalyzer that uses is the most active, and can obtain high molecular weight elastomer in very wide ethylene content scope.
Test A 14-A 16Illustrating with phenyl, trimethyl silyl methyl or oxo bridge replaces second kind of luxuriant muriate of zirconium that activity or molecular weight of product are not almost influenced.
The table II is the performance of two kinds of catalyzer relatively, promptly by the supported catalysts of two kinds of luxuriant preparations of the most active zirconium of the present invention with by a kind of performance of catalyzer of the best luxuriant preparation of zirconium that is used for comparison.Test B 1-B 3Use relatively that catalyzer explanation high reactivity and high molecular can not obtain simultaneously, this is for being especially accurately than low ethylene content.When ethylene content is lower than 70wt%, test B 1-B 3The molecular weight of comparison catalyzer products therefrom much lower.Use catalyzer of the present invention can avoid this problem.Even though do not obtain the second best in quality EPC(B with not adding additional Lv oxane in the catalyzer slurries of the present invention yet 11), but active obviously reduction for obtaining high reactivity, needs to add Fu Jia Lv oxane.In all these tests, resemble that product stains reactor the unsupported catalyst.Because heat release causes high temperature, the molecular weight distribution broad during reaction beginning.With unsupported catalyst relatively, though some reduction of activity of such catalysts on the carrier (by gram-Zr calculating), concerning industrial production, by the activity of gram-calculated 1000 gram/grams-catalyzer/hour more than think good.
The explanation of table III improves with the carried catalyst performance of prepolymerization form.For these catalyzer, although obtain excellent high reactivity, the intensification during beginning is actually and can not finds.And with the situation contrast that the catalyzer of table I and table II always is stained with wall, these catalyzer do not stain reactor, and in most cases granular product by each polymer spherical granulometric composition.Here it is uses this class catalyzer to carry out the remarkable advantage of slurry polymerization.
Figure 891063447_IMG12
Figure 891063447_IMG13
Figure 891063447_IMG16
Test zirconium luxuriant catalyst component
A 1Two (cyclopentadienyl) zirconium dichlorides of dimethylated methylene base bridging
A 2Two (cyclopentadienyl) zirconium dichlorides of dimethyl silicylene bridging
A 3Two (benzyl ring pentadienyl) zirconium dichloride
A 4Two (methyl cyclopentadienyl) zirconium dichlorides of dimethyl silicylene bridging
A 5Two (indenyl) zirconium dichlorides of ethylidene bridging
A 6Two (indenyl) zirconium dichlorides of dimethyl silicylene bridging
A 7-A 9Two (n-butyl cyclopentadienyl) zirconium dichloride
A 10Two (normal-butyl tetrahydro indenyl) zirconium dichloride
A 11Two (tetrahydro indenyl) zirconium dichloride
A 12Two (tetrahydro indenyl) zirconium dichlorides of ethylidene bridging
A 13Two (tetrahydro indenyl) zirconium dichlorides of dimethyl silicylene bridging
A 14Two (tetrahydro indenyl) phenylbenzene zirconium
A 15Two (tetrahydro indenyls) two (trimethyl silyl methyl) zirconium
A 16Bis oxide (two (tetrahydro indenyl) zirconium chloride)
B 1-B 3Two (n-butyl cyclopentadienyl) zirconium dichloride
B 4-B 8Two (tetrahydro indenyl) zirconium dichloride
B 9-B 12Two (tetrahydro indenyl) phenylbenzene zirconium
B 13Two (tetrahydro indenyl) zirconium dichlorides of ethylidene bridging
B 14-B 17Two (tetrahydro indenyl) zirconium dichlorides of dimethyl silicylene bridging
C 1-C 10Two (tetrahydro indenyl) zirconium dichloride
C 11-C 13Two (tetrahydro indenyl) zirconium dichlorides of dimethyl silicylene bridging
The explanation of table
Zirconium is luxuriant: the general formula of the luxuriant component of zirconium in the catalyzer
Catalyzer: PP(nnn) THIZ contains (THI) 2ZrCl 2With the ethene pre-polymerized catalyst, be the nnn% of its not prepolymerization weight, PP(nnn) STHI is identical therewith, but contains Me 2Si(THI) 2ZrCl 2
Catalyzer
ZirC: on carrier or pre-polymerized catalyst in the luxuriant wt% of zirconium
MAO: on carrier or pre-polymerized catalyst in methyl Lv oxane wt%
Mg: catalyst consumption in the test
MAOML: the amount of methyl Lv oxane (in toluene, concentration is 1M), as the promotor that is added in the slurries.
25%
TEALML: the amount of triethyl aluminum (25wt% is in hexane), as the scavenging agent promotor
C 2Pound: the supercharging of the ethene of using in the test, on the vapour pressure of propylene.
T ℃: temperature of reaction
Heat up ℃: the number of degrees that observed temperature raises when adding catalyzer
△ T ℃: the number of degrees that observed temperature raises when adding catalyzer
Output g: the dried polymer weight that from reactor, reclaims
Active
Kg/g-Zr/h: the polymkeric substance kilogram that every gram zirconium per hour obtains in the reaction is counted activity
Kg/g-Cat/h: the polymkeric substance kilogram number that every gram catalyzer per hour obtains in the reaction
C 2%: the weight % of ethene in the polymerisate presses ASTM D3900 at every turn
Measure.
Mw10 3: the weight-average molecular weight of product, measure (thousands of) by DRI
MWD: molecular weight distribution, represent with the weight-average molecular weight and the ratio of number-average molecular weight
ML 1+8, 127 ℃: mooney viscosity, all press ASTM D1646 at every turn and measure.

Claims (20)

1, prepare the elastomeric method of EPC with slurry polymerization, this method comprises:
Add a certain amount of 'alpha '-olefin monomers in reactor, and it is under the certain pressure, this pressure is enough to make alpha-olefin to use as polymerization diluent with liquid form, and the EPC elastomerics is insoluble to wherein on substantially;
In described 'alpha '-olefin monomers thinner, add a certain amount of ethene, be enough to make in the liquid phase of reactor keep required ethylene/alpha-olefin ratio;
Add metallocenes/Lv oxane catalyst system in monomer mixture, wherein the metallocenes component in the catalyzer has general formula:
M is zirconium, titanium or hafnium in the formula; Each R 1Be respectively C 1-C 20The alkyl of linear or side chain or ring alkylidene group, R 2Be C 1-C 6Linear, side chain or the cyclic alkylidene group, the silicylene that alkyl replaces, or the inferior silicon-carbon alkyl that replaces of alkyl, each X represents oxygen or the alkyl in the luxuriant dimer of zirconium that halogenide, hydride, oxo bridge connects respectively, " b " be 0 or 1 and " Y " be 2,3 or 4 integer;
The sufficiently long time of olefinic monomer mixture reaction, make described ethene and 'alpha '-olefin monomers copolymerization generate the EPC elastomerics.
2, according to the process of claim 1 wherein that M is that zirconium and the luxuriant/Lv of described zirconium oxane catalyst system are present on the catalyst support material, preferably silica gel and/or preferred described Lv oxane are methyl Lv oxanes.
3, according to the method for claim 1 or 2, wherein 'alpha '-olefin monomers is propylene, butene-1 or their mixture.
4, according to the method for above-mentioned arbitrary claim, wherein " b " is 0, the R of the luxuriant component of zirconium in the catalyzer 2Do not exist; The R of the luxuriant component of zirconium in the catalyzer wherein 2It is ethylidene; And/or the R of the luxuriant component of zirconium in the catalyzer wherein 2It is the dimethyl silicylene.
5, according to the method for above-mentioned arbitrary claim, wherein the luxuriant component of the zirconium of catalyzer has general formula:
" Z " is 0 to 2 integer.
6, according to the method for arbitrary claim of claim 2 to 5, wherein in the catalyzer mol ratio of aluminium and zirconium in 10 to 5000 scopes.
7, according to the method for above-mentioned arbitrary claim, wherein polymerization temperature is in 0-80 ℃ of scope.
8, prepare the method for ethene-alpha-olefin elastomer copolymer with slurry polymerization, comprise the following steps:
Add a certain amount of 'alpha '-olefin monomers in reactor, and it is under the certain pressure, this pressure is enough to make described alpha-olefin to use as polymerization diluent with liquid form;
In described alpha-olefine polymerizing thinner, add a certain amount of ethene, make the required ethylene/propene ratio of maintenance in the reactor liquid phase and;
In monomer mixture, add carrier metallocenes/Lv oxane catalyzer, this catalyzer closes with ethene or a kind of alpha-olefin copolymer, gross weight with catalyzer and solid support material is a benchmark, its weight increases by 50% at least, and wherein the inorganic oxide handled of support of the catalyst Shi Lv oxane and the metallocenes component of catalyzer have general formula:
M is zirconium, titanium or hafnium in the formula; Each R 1Be respectively C 1To C 20The alkyl of linear or side chain or ring alkylidene group, R 2Be C 1To C 6Linear, side chain or the cyclic alkylidene group, the inferior silicon-carbon alkyl that silicylene that alkyl replaces or alkyl replace, each X are respectively luxuriant dimeric oxygen of zirconium or the alkyl that halogenide, hydride, oxo bridge connect, " b " be 0 or 1 and Y be 2,3 or 4 integer;
The sufficiently long time of olefinic monomer mixture reaction, make described ethene and 'alpha '-olefin monomers carry out copolymerization and generate the EPC elastomerics.
9, method according to Claim 8, wherein M is that the luxuriant component of zirconium of zirconium and catalyzer has general formula:
Figure 891063447_IMG5
Each R in the formula 1It is respectively alkyl with linear or side chain of 1 to 20 carbon atom; " Z " is 0 to 2 integer, and each X is respectively alkyl, aryl, hydride or halogenide.
10, according to claim 5 or 9 and comprise the method for the feature that arbitrary claim of claim 2 to 7 is asked.
11, a kind of liquefied olefines slurry polymerization that is used for prepares the elastomeric prepolymerization catalysis of EPC agent, and it contains:
A kind of dry that cross and that Yong Lv oxane was handled inorganic carrier, the zirconium of structure is luxuriant below then adding:
Figure 891063447_IMG6
Each R in the formula 1Be respectively C 1-C 20Linear, side chain or the cyclic alkyl maybe can form the C of condensed ring system base 2-C 4The ring alkylidene group; R 2Be C 1-C 6Linear, side chain or the cyclic alkylidene group, Si 1-Si 2The inferior silicon-carbon alkyl that silicylene that alkyl replaces or alkyl replace; Each X is respectively halogenide, hydride, luxuriant dimeric oxo bridge of zirconium or alkyl; " Y " be 2,3 or 4 and " b " be 0 or 1;
Then carry out prepolymerization and handle, make catalyst weight increase 50wt% at least with ethene or a kind of alpha-olefin.
12, according to the pre-polymerized catalyst of claim 11, wherein inorganic carrier is that the silica gel ， Lv oxane of crossing 100-1000 ℃ of drying is a methyl Lv oxane.With the ratio of silica gel in 1: 1 to 1: 10 scope (weight ratio), and/or the mol ratio of aluminium and zirconium is in the 1-500 scope.
13, according to the pre-polymerized catalyst of claim 11 or 12, wherein the weight of prepolymerization increase is in the 50-500wt% scope.
14, according to the pre-polymerized catalyst of arbitrary claim of claim 10 to 13, wherein zirconium is luxuriant is two (tetrahydro indenyl) zirconium dichlorides, two (tetrahydro indenyl) zirconium dichlorides of dimethyl silicylene or ethylenebis (tetrahydro indenyl) zirconium dichloride.
15, according to the pre-polymerized catalyst of above-mentioned arbitrary claim, wherein, wash pre-polymerized catalyst with hydro carbons after the prepolymerization.
16, the elastomeric method of a kind of preparation EPC comprises: ethene contacts with metallocenes/aluminoxane catalyst system with a kind of 'alpha '-olefin monomers under polymerizing condition, and wherein the metallocenes component of catalyzer has general formula:
M is zirconium, titanium or hafnium in the formula; Each R 1Be respectively C 1-C 20Linear or branched-chain alkyl or ring alkylidene group; R 2Be C 1-C 6Linear, side chain or the cyclic alkylidene group, the inferior silicon-carbon alkyl that silicylene that alkyl replaces or alkyl replace; Each X is respectively oxygen or an alkyl in halogenide, hydride, the oxo bridge luxuriant dimer of zirconium even; " b " be 0 or 1 and " Y " be 2,3 or 4 integer.
17, according to the method for claim 16, wherein M is a zirconium, and the luxuriant/Lv of described zirconium oxane catalyst system is present on the catalyst support material, and preferably on the silica gel, the amount of zirconium metal is the 0.02-5.0% weight of total catalyst weight.
18, according to the method for claim 16 or 17, wherein in the catalyzer mol ratio of aluminium and metal (M) in the 1-200 scope.
19, according to the method for arbitrary claim of claim 16 to 18, wherein said method is a continuous processing.
20, according to the method for the arbitrary claim of claim 16 to 19, wherein said method is continuous slurry process and uses a certain amount of hydrocarbon, under reaction pressure, be enough to make described hydrocarbon to use as polymerization diluent with liquid form, and the EPC elastomerics is insoluble to wherein on substantially, at least partly or entirely is 'alpha '-olefin monomers as the preferred hydrocarbon of polymerization diluent.
CN89106344A 1988-06-16 1989-06-16 Prepare the elastomeric method of high molecular weight ethylene a-olefin with metallocene alumoxane catalyst Pending CN1042160A (en)

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